Multifunctional detergent materials

ABSTRACT

A multifunctional detergent material, useful in laundry and cleaning product compositions, containing functional ingredients including a condensed phosphate material and a silicate material, and optionally other inorganic materials, such as carbonate and sulfate. The condensed phosphate material forms an amorphous phase containing polyphosphates, while the silicate material is present as crystalline particulate. The composition can be used to provide multiple functions for laundry and cleaning products in a single ingredient, including the functions of a builder, a filler, and an alkaline source.

This application claims the benefit of No. 60/096,758, filed Aug. 17,1998.

FIELD OF THE INVENTION

This invention relates to a single multifunctional detergent materialcomprising inorganic compounds containing inorganic oxides used inlaundry and cleaning products.

BACKGROUND OF THE INVENTION

Conventional laundry and cleaning products contain numerous inorganiccompounds, usually in a form comprising one or two inorganic oxides.Each of such compounds performs one or more functions, such as thefunctions of a builder, a conditioner, an alkaline agent, a filler, acarrier, and a neutralizing agent, in the detergent and/or in theprocess for its manufacture. A high number of raw materials which can beused for a particular laundry or cleaning product formulation, impartingtheir respective functions, can account for a considerable portion ofthe cost of producing the detergents. Each raw material has its separateprocessing cost, transportation cost, operating expense, and other fixedor variable costs.

The processing of laundry and cleaning products has generally involvedthe separate addition of the inorganic oxides in the process for makingthe product, involving the storage, feeding, and control of theinorganic oxide stock into the process stream to deliver the targetlevel of inorganic oxide actives into the product. Depending upon theamount or mass rate of a stock to be used, and the physical and flowproperties and chemical purity of the stock, the actual level ofinorganic oxide active can vary more or less than the target level inthe detergent product. Consequently, manufacturers incur a significantcost and expense in installing feeders and controllers to deliver theappropriate amount and rate of stock material, and in analyzing rawmaterial stock and finished detergent products for the appropriate levelof inorganic oxide active.

The most common inorganic oxides that are found in inorganic compoundsthat are used to make laundry and cleaning products are phosphorus oxide(P₂O₅), sodium oxide (Na₂O), carbon dioxide (CO₂), and silica (SiO₂).Other additional oxide ingredients can include boron oxide (B₂O₃) andsulfur trioxide (SO₃). Usually, these inorganic oxides are combined withsodium oxide (Na₂O) or other alkali or alkali metal oxide to form andmake the commercially-available inorganic compounds that can beprocessed into laundry and cleaning. For example, the silica can bedelivered into the product in the form of amorphous or crystallinesilicate having the general formula xSiO₂:Na₂O, where x is about 1 toabout 3.8. Silica can also be introduced as an aluminosilicates such asa zeolite, and as a layered silicate. Phosphorous oxide is commonlysupplied in the form of hydrated or anhydrous sodium tripolyphosphate(Na₅O₁₀P₃), tetrasodum pyrophosphate (Na₄O₇P₂), and orthophosphate(Na₃O₄P).

The pure inorganic oxides and/or inorganic compounds are generallyobtained from nature in the form of minerals and ores. Natural sourcesof silica are silica sand, quartzite, and cristobalite. A natural sourceof phosphorous oxide is phosphoric rock. A natural source of sodiumcarbonate is trona. Natural sources of sodium sulfate (Na₂SO₄) aremirabilite and thenardite.

The natural sources of inorganic oxides may contain impurities or inertby-products which are normally removed from the natural material beforeor during converting to the inorganic compound commercial stock. Sodiumtripolyphosphate (STPP), for example, is made by first reacting groundphosphoric rock with sulfuric acid to form phosphoric acid; silica(SiO₂) is an impurity of this reaction which is ordinarily filtered fromthe phosphoric acid. In turn, the phosphorus acid is reacted with sodiumcarbonate to form STPP. The silica impurity, though eliminated from theSTPP, is nevertheless a material which is commonly present in detergentformulation in some other form.

Sodium carbonate, a common source of Na₂O, can be obtained from thetreatment of trona mineral by a process including grinding, diluting,filtering to eliminate compounds considered as impurities (includingagain silica), and crystallizing, to obtain the sodium carbonate. Thesodium silicate can be obtained from melt reacting a mixture of silicasand and sodium carbonate at high temperatures in a furnace.

Silica is an impurity compound in these natural sources of inorganicoxides, and the processing required to eliminate the silica impurityfrom each individual natural raw material contributes to some of thecost of the detergent chemical compounds, and consequently to the finaldetergent.

U.S. Pat. No. 5,707,960, issued to Fukuyama et al. On Jan. 13, 1998,discloses an amorphous sodium silicate-metal sulfate composite powderfor use as a detergent builder. The powder is made by heat fusing ametal sulfate, silica, and sodium carbonate or sodium hydroxide at atemperature and time sufficient to fuse the SiO2; cooling the fusedmixture into cullet, and grinding the cullet into the composite powder.

WO 9902643 (Vitro Corporation) discloses a process for making amultifunctional component for detergent compositions, by mixing naturaland treated minerals containing the essential oxides for the detergentcompositions, and reacting the mixture in a furnace, thereby forming apowder or glass containing the essential oxides.

However, phosphate builders such as STPP and TSPP are important laundryand cleaning product ingredients, and are widely used in many parts ofthe world as the principle detergent builder. Consequently there remainsa need to develop improved functional raw materials for laundry andcleaning products, and for processes to make the same.

It is therefore an object of the present invention to provide a singlemultifunctional detergent material that can include several, andpreferably three or more, of the typical inorganic oxides normallyincluded in laundry and cleaning product, and can have the productfunctions of these inorganic oxides, such as the functions of a builder,a conditioner, a filler, an alkaline agent, a carrier, or a neutralizingagent.

It is also an object to provide a multifunctional detergent material(hereinafter, “MFDM”) containing multiple inorganic oxides, in a singlematerial which is less expensive to manufacture and to use in the makingof laundry and cleaning products, and which eliminates the need to addeach raw material separately into the process for making the laundry orcleaning product. The addition of each raw material in the process caninclude the unloading, storage, feeding, and metering of the rawmaterial.

It is yet another object to provide a single multifunctional detergentmaterial which enables accurate control of the delivered level ofinorganic oxides into a particular laundry or cleaning productformulation.

It is also an object to provide a multifunctional detergent material fordetergent formulations, which can provide unique product performanceproperties, compared to conventional inorganic oxide mixtures andcomponents.

Another object of the present invention is to provide a laundry orcleaning composition or component thereof, containing or made using asingle multifunctional detergent material that contains many of therequired inorganic oxides for the detergent formulations.

These and other objects and advantages of the product and the process ofthe present invention will be apparent from the following descriptionand specific examples of the invention.

SUMMARY OF THE INVENTION

The present invention provides a multifunctional detergent material,useful in laundry and cleaning product compositions, comprising at leasttwo functional inorganic oxide ingredients selected from phosphorousoxide and silicon dioxide. Preferably the material comprises a phosphatecomponent comprising phosphorus oxide (P₂O₅) and sodium oxide (Na₂O),and a silicate component comprising silicon oxide (SiO₂) and sodiumoxide. The phosphate component comprises a linear polyphosphate, acyclic metaphosphate, or mixtures thereof, in addition to other lowerphosphates such as orthophosphate and pyrophosphate.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows an Ion Chromatogram of a multifunctional detergent materialof the present invention, according to Example 3, showing thepolyphosphate and other phosphate species contained in the material.

FIG. 2 shows an X-ray Diffraction pattern of a multifunctional detergentmaterial of the present invention, according to Example 3, showing theamorphous polyphosphate and crystalline silicate species contained inthe material.

FIG. 3 shows an Ion Chromatogram of a base granule made using amultifunctional detergent material of the present invention, accordingto Example 4, showing the polyphosphate and other phosphate speciescontained in the base granule.

DETAILED DESCRIPTION OF THE INVENTION

The present invention provides a multifunctional detergent material,useful in laundry and cleaning product compositions, comprising a solidsolution of at least two functional inorganic oxide ingredients selectedfrom phosphorous oxide and silicon dioxide. Preferably the materialcomprises a condensed phosphate component comprising phosphorus oxide(P₂O₅) and sodium oxide (Na₂O), and a silicate component comprisingsilicon oxide (SiO₂) and sodium oxide.

The phosphorus oxide ingredient can be expressed by the formula(Na₂O)_(a)(P₂O₅)_(b), where the ratio of a:b is from about 0 to about 3,and more preferably about 0.8 to about 2. The phosphorous oxideingredient (hereinafter also referred to as the condensed phosphatecomponent of the MFDM) can comprise a variety of phosphate species thatinclude: ultraphosphates, which are randomly (amorphous) or ordered(crystalline) interconnected chains and/or rings, and metaphosphates,which are ring structures, that have a ratio of a:b of from above 0 toabout 1; polyphosphates, which are linear chains of P-O-P units, thathave a ratio of a:b of from about 1 to about 2, and include sodiumtripolyphosphate (STPP) having a structure Na₅O₁₀P₃ and a ratio a:b of5/3; tetrasodium pyrophosphate (TSPP) having a structure Na₄O₇P₂ and aratio a:b of 2:1; trisodium orthophosphate having a structure Na₃O₄P anda ratio a:b of 3:1; and mixtures thereof. Preferably the MFDM comprisesa condensed phosphate component selected from the group consisting oflinear polyphosphates, cyclic metaphosphates, and mixtures thereof.

The linear polyphosphate has a structure of formula I:

where m can range from 3-100, and preferably from 3-30, and where M isselected from Na, K, Li, and H, and mixtures thereof, and is preferablyNa. When m is 3, the linear polyphosphate is sodium tripolyphosphate.

The cyclic metaphosphate has a structure of formula II:

where n can range from 3-20, and preferably from 3-10, and where M isselected from Na, K, Li, and H, and mixtures thereof, and is preferablyNa.

Linear polyphosphates and cyclic metaphosphates having m greater than 3are also referred to herein as higher polyphosphates.

Preferably, the MFDM of the present invention comprises from about 10%to about 99% percent by weight of a mixture of the linear polyphosphateand cyclic metaphosphate. Typically the weight ratio of polyphosphate tometaphosphate is from about 40:1 to about 1:1, and more preferably about20:1 to about 4:1. The MFDM can also contain other phosphate materialssuch as orthophosphate and pyrophosphate, or other extremely long (mgreater than 100) polyphosphates.

The silicon oxide ingredient is generally present as a silicateexpressed by the formula (SiO₂)_(x)(Na₂O)_(y), where the ratio of x:y isfrom about 0.5:1 to about 4:1, more preferably about 0.7:1 to about1.3:1. The silicon oxide ingredient can also be referred to as thesilicate component of the MFDM.

As previously discussed above, a third inorganic oxide contained in theMFDM is disodium oxide, or Na₂O. It is present in combination with thephosphorous oxide to form the condensed phosphate component, and withthe silicon oxide to form the silicate component, but can also bepresent as a free component.

In the presence of moisture, the linear polyphosphates and cyclicmetaphosphates can be hydrolyzed to the lower phosphates, includingorthophosphate, pyrophosphate, and sodium tripolyphosphate. Thishydrolysis can be accelerated by higher temperatures (generally aboveabout 39° C.), and at extreme acidic or alkali conditions of pH.Consequently, the MFDM of the present invention, can also comprise asolid solution of a condensed phosphate component and a silicatecomponent wherein a substantial portion of the polyphosphates and/ormetaphosphates present have been hydrolyzed to the lower phosphates,including STPP and TSPP. Preferably the weight average chainlength(n_(avg)) of the polyphosphates is greater than 6, more preferablygreater than 13, and most preferably greater than 20.

The MFDM comprises from about 5% to about 60%, more preferably fromabout 10% to about 50%, by weight of condensed phosphate componentexpressed as P₂O₅, and from about 5% to about 50%, more preferably fromabout 15% to about 50%, by weight of silicate expressed as SiO₂.Preferred embodiments of MFDM comprise the phosphorus oxide (P₂O₅) andthe silicon oxide (SiO₂) ingredients at a weight ratio of from about1:20 to about 12:1, more preferably from about 1:5 to about 3:1. TheMFDM can comprise from about 5% to about 80%, more preferably from about10% to about 60%, by weight the condensed phosphate component, and fromabout 10% to about 60%, more preferably from about 15% to about 50%, thesilicate component

In the MFDM, the alkali metal sodium (Na) can be replaced in part or intotal with another alkali metals, such as lithium (Li) or potassium (K),or alkali earth metals, such as calcium (Ca) or magnesium (Mg).

In one preferred embodiment, the MFDM can be described as a solidsolution, wherein the condensed phosphate component and the silicatecomponent are miscible and form a single solid phase. One component willform a continuous solid phase, having the other component as a dispersedsolid phase therein. The miscibility of the condensed phosphatecomponent with the silicate component will depend upon the proportion ofthe SiO₂, P₂O₅ and Na₂O contained in reaction mixture. Preferably, thecontinuous solid phase comprises the condensed phosphate component, andthe dispersed solid phase comprises the silicate component. Thecontinuous solid phase can further contain therein optional otherinorganic material, such as other inorganic oxides and inorganiccompounds. A preferred MFDM comprises a continuous solid phase of thecondensed phosphate component having dispersed therein the silicatecomponent.

In another preferred embodiment, the MFDM can be described as a mixtureof solid particle comprising the condensed phosphate component and thesilicate component which are immiscible one with the other. Theseparate, immiscible components easily separate into distinct particlesupon crushing or grinding of the cooled solid components.

The condensed phosphate component can be in an amorphous phase or acrystalline phase, though more commonly and preferably the continuouscondensed phosphate component is amorphous. The silicate component canalso be in an amorphous phase or a crystalline phase, though morecommonly and preferably the dispersed silicate component is crystalline.In general, the dispersed silicate component of the present inventionwill dissolve more quickly and generate less silicate insolublematerial, compared to compositions containing conventional amorphous orcrystalline silicate that is processed into the detergent composition byconventional methods.

Additional inorganic oxides can also be optionally included in the MFDM.Preferably, such optional inorganic oxide ingredients are also commonlyand preferably used in laundry and cleaning formulations to provide animportant function, such as bleaching and stabilizing. Preferredexamples of optional inorganic oxides include boron oxide (B₂O₃) andsulfur oxide (SO₃), commonly in the form of sodium sulfate (Na₂SO₄).When included in the MFDM, the level of sodium sulfate (or other saltthereof) can be present at from about 1% to about 50%, by weight,depending upon the need for filler or other functionality in theformulation. Because of the sulfur oxide content in silica, phosphoricrock, trona, and other raw mineral ingredients, the MFDM can contain upto 1% or more of sodium sulfate without having to add sodium sulfate oradditional source of sulfur oxide to the raw ingredients chargedtogether to make the MFDM.

Making of MFDM

The MFDM of the present invention is made by the mixing together of twoor more natural or partially treated (ground or comminuted) primary rawmaterials or minerals, in proportions according to the needs of aspecific detergent formulation, raising the mixture to a reactingtemperature, such as by introducing the mixture into a furnace, reactingthe mixture at the reacting temperature, and forming the MFDM. One ormore of the materials can be in the molten state upon mixing of theother ingredients. The process system for making the MFDM can be batchor continuous.

The primary raw materials or minerals contains a source of phosphorusoxide, a source of silicon oxide, and a source of disodium oxide.Preferred sources of phosphorus oxide are phosphoric rock and phosphorusacid. Preferred sources of silicon oxide are silica sand, as well asquartzite and cristobalite. The disodium oxide is needed to form thevarious phosphate and silicate species, and can be obtained from trona,sodium carbonate, and sodium hydroxide.

The raw materials are balanced to provide a MFDM containing a desired orpreferred ratio and level of phosphate (P₂O₅) to silica (SiO₂) for usein laundry and cleaning products. Other inorganic raw materials usefulin laundry and cleaning products can, and preferably are, included inthe mixture, such as an alkali oxide, preferably Na₂O, and carbonate.

In a typical process, the sources of phosphorus oxide, silicon oxide,and disodium oxide are typically mixed together as ground or communitedparticles. The mixture of phosphorus oxide, silicon oxide, and disodiumoxide can be further ground as needed, and then charged into a furnaceor equivalent vessel capable of increasing the temperature of themixture to a reacting temperature. The reacting temperature includes atemperature at which phosphous oxide is dehydrated and “polymerizes”into the ultraphosphates, polyphosphates and metaphosphates. Thereacting temperature can also be a fusing temperature at which thesilicon dioxide can fuse into silicates. Longer reacting time and higherreacting temperature generally increases the extent of polymerization ofthe phosphorus oxide into the linear polyphosphates and cyclicmetaphosphates toward an equilibrium which is dependent upon the ratioof sodium oxide and P₂O₅ in the reaction mixture. Generally the reactingtemperature results in a mixture that is molten. Typical temperaturesfor reacting and/or heat fusing the mixture are from about 600° C. toabout 1500° C., more preferably from about 900° C. to about 1300° C.,and most preferably from about 1000° C. to about 1200° C. The reactingtemperature should be selected to avoid any decomposition of anyoptional inorganic materials present. For example, sodium sulfatedecomposes at temperatures above about 1300° C.

It is economically preferred that the reacting of the mixture is for atime as short as possible. The time should be sufficient to effectfusing of the components, and to ensure a sufficiently uniform moltenmixture. Such time generally takes 10 hours or less, and preferably fromabout 1 hour to about 5 hours.

Prior to forming the final MFDM product, other optional materials,generally in the form of powders or glasses, can be admixed or dissolvedwith or into the molten, reacted mixture after exiting the furnace.

The resulting MFDM can then be formed into a powder, a glass, or aliquid. The powder can be prepared by cooling the fused, molten mixtureinto a cullet by any means, such as by air cooling, cooling within thefurnace, or by water cooling. The solidified cullet can then be groundinto a powder of the appropriate particle size and distribution by knownmeans. Alternatively, a powdered MFDM can be formed by atomizing themolten mixture into droplets and cooling the droplet below its glasstemperature. The powder is generally hydratable and hygroscopic.Preferably the powder particles range in size from about 5 microns toabout 1500 microns, and more preferably about 50 microns to about 1000microns. A preferred powder has particles substantially having a meanparticle size from about 200 microns to about 1000 microns.

The resulting MFDM can be formed into a glass or a liquid by dissolvingthe molten mixture to an extend with water or other suitable solvent,whereby the glass or liquid solution of the MFDM can be obtained atambient or storage temperatures.

The process can optionally, though preferably, comprise the further stepof removing impurities and inert materials from the reacted mixture,prior to or subsequent to forming the powder or glass MFDM. Theinorganic raw materials can also consist of fully treated inorganicmaterials which have been processed to remove impurities and processedinto a solid or liquid form suited for addition to detergent products.However, the treatment to remove impurities of the several fully treatedraw materials is unnecessary when practicing the present invention,since a single process step of removing impurities can be used after theraw material mixture has been reacted. Partial treatment, such as anacid or alkaline attack on the natural raw material, or as by grinding,sieving and screening, can be used. In general, it is unnecessary totreat the raw materials of the MFDM to eliminate a compound or elementthat can be used in the laundry or cleaning product. In the productionof carbonate from the natural raw material trona, silica is usuallyremoved as an impurity. In the present invention, however, whencarbonate is included as a raw material to make the MFDM, the silicapresent is used to form a part of the silicate (SiO₂) of the MFDM. Notonly is it unnecessary to remove the silica from the trona as animpurity, but that in fact it is preferred to use the raw trona since itprovides an additional source of silica for the MFDM.

Furthermore, if a specific structure for the product is needed forspecific purposes of the detergent producer, the process can furthercomprise the step of annealing the MFDM.

The obtained multifunctional detergent material is soluble and/ordispersible in water, allowing the material to perform the functions ofany two or more of a builder, a conditioner, a filler, an alkalineagent, and carrier, in laundry and cleaning formulations and in amanufacturing process for making such formulations, at less expense inmaterial cost than the individual raw materials that are normally usedand that are replaced by the MFDM.

The MFDM allows the detergent producer to avoid paying for the charge ofhandling and transporting multiple raw materials, and for transportingsome unneeded volatile or gaseous components that are present in the rawmaterials, such as the CO₂ that is chemically present in sodiumcarbonate.

Use of MFDM in Laundry and Cleaning Products

The MFDM of the present invention is particularly useful as aningredient in laundry and cleaning products, and can provide multiplefunctions for laundry and cleaning products in a single ingredient,including the functions of a builder, a conditioner, an alkaline agent,a filler, a carrier, and a neutralizing agent. The MFDM is particularlyeffective in granular and liquid detergent products in view of itsunique and surprising properties.

When formulated into laundry and cleaning products, the MFDM providessubstantially equivalent cleaning, in terms of stain removal andwhiteness maintenance, compared to detergent formulations prepared fromconventional raw materials which deliver equivalent levels of silicate(SiO₂), phosphate (P₂O₅) and alkalinity (Na₂O). It has also been foundthat the MFDM of the present invention is capable of controlling Ca++ inthe wash solution, to the same extent as STPP on an equal P₂O₅ basis,thereby inhibiting the precipitation of anionic surfactants by the Ca++,to about the same extent as STPP.

Surprisingly, laundry and cleaning product formulations containing aMFDM that comprises a dispersed silicate component yield less insolubleand precipitated silicate material into the wash solution as compared toconventional formulations containing equivalent levels of theconventional silicate material (water glass) and processed byconventional methods. Without being bound by any theory, it is believedthat the silicate component dissolves more rapidly and is dispersedwithin the wash solution, compared to amorphous or crystalline silicatecontained in products made by conventional methods.

The laundry and cleaning formulation containing the MFDM also provides asubstantially equivalent level of hardness sequestration compared to aformulation built with either pyrophosphate or tripolyphosphate, orboth, on an equal P₂O₅ basis. It is also well known that conventionalformulations built with pyrophosphate experience a reduction in buildereffectiveness as the level of water hardness in the wash water increasesand the product is used at close to the underbuilt conditions. Thisreduction in builder effectiveness is called the “pyro dip”. The pyrodip represents those molar ratios of builder capacity to hardnessapproaching and below 1:1 (compared to an overbuilt condition where themolar ratio of builder to hardness is greater than 1:1) where thepyrophosphate complex is insoluble and precipitates. The effect of thepyro dip in the washing process is an increase in soil redeposition onthe clothes. It has been found that the present MFDM is a more effectivebuilder than pyrophosphate at such near-underbuilt and underbuiltconditions, and there is not seen an increase in soil redeposition atequivalent levels of MFDM on an equal P₂O₅ basis. It is believed thatthe presence of the polyphosphates metaphosphates in the MFDM providesthis benefit. It has been known to add low levels of polyphosphate(commercially available from FMC Corporation as “Glass H”) topyrophosphate and orthophosphate-built detergents to improveanti-redeposition due to the pyro dip. The present invention provides asingle multifunctional detergent material with a builder capacityequivalent to pyrophosphate and the anti-redeposition (pyro dip)protection of a conventional polyphosphate.

Laundry and Cleaning Products Containing MFDM

The present invention also includes laundry and cleaning productscontaining the MFDM. These products can be in a variety of forms,including granules, fine powders, liquids, gels, pastes, bars, solidabrasives, etc.

The present invention provides laundry or cleaning detergentcompositions, including granular, powdered, paste, and bar compositions,and components thereof, comprising, by weight, from 1-45% a detergentsurfactant, and from 3-95% the multifunctional detergent material.

A preferred laundry detergent composition of the present inventioncomprises by weight from 1-45% detergent surfactant and from 3%-50% of acondensed phosphate component selected from the group consisting of thelinear polyphosphates of the formula I, the cyclic metaphosphates of theformula II, and mixtures thereof.

Detergent surfactants can include anionic surfactants, cationicsurfactants, nonionic surfactants, amphoteric surfactants, and mixturesthereof.

The anionic surfactant can be selected from alkylbenzene sulfonate,alkyl sulfate, alkyl ethoxy ether sulfate, and mixtures thereof.Preferred are alkylbenzene sulfonate and alkyl sulfate.

Alkylbenzene sulfonates are salts of alkylbenzene sulfonic acid with analkyl portion which is linear or branched, preferably having from about8 to about 18 carbon atoms, more preferably from about 9 to about 16carbon atoms. The alkyl of the alkylbenzene sulfonic acid preferablyhave an average chain length of from about 10 to about 14 carbon atoms,more preferably from about 11 to about 13 carbon atoms. The alkyl arepreferably saturated. Branched or mixed branched alkylbenzene sulfonatesare known as ABS. Linear alkylbenzene sulfonates, known as LAS, are morebiodegradable than ABS, and are preferred for the subject inventioncompositions. The salt can be sodium, potassium, and ammonium,preferably sodium. Alkylbenzene sulfonates and processes for making themare disclosed in U.S. Pat. Nos. 2,220,099 and 2,477,383, incorporatedherein by reference.

Alkyl sulfates (AS) are the alkali salts of alkyl sulfuric acids,preferably having carbon chain lengths in the range of from about C₁₀ toabout C₂₀. Alkyl sulfates having chain lengths from about 12 to about 18carbon atoms are preferred. AS surfactants preferably have average chainlengths from about 12 to about 14 carbon atoms. Especially preferred arethe alkyl sulfates made by sulfating primary alcohol derived fromcoconut or tallow and mixtures thereof. Salts can be sodium, potassium,lithium, ammonium, and alkylammonium salts. Preferred salts of alkylsulfates are sodium and potassium salts, especially sodium salts.

Alkylethoxy ether sulfate (AES) surfactants useful in the subjectinvention compositions have the following structure:R′″O(C₂H₄O)_(x)SO₃M, where R′″ is alkyl, preferably saturated linearalkyl, of from about 10 to about 20 carbon atoms, x is on average fromabout 1 to about 9, preferably from about 1 to about 7, more preferablyfrom about 2 to about 5, especially about 3, and M is a water-solublecation, preferably sodium or potassium. The AES surfactants aretypically obtained by sulfating alkyl ethoxy alcohol with gaseous SO₃ ina falling film reactor, followed by neutralization with NaOH, as is wellknown in the art.

In addition to the MFDM, optional supplemental builders can be added tothe composition. The optional builders can be contained at levels offrom about 1% to about 35% by weight in the composition. Such optionalbuilders can include:

1. Phosphate-containing detergent builders, including tripolyphosphates,pyrophosphates, glassy polymeric meta-phosphates, and alkylphosphonates. When other phosphate-containing detergent builders, thedetergent composition can comprise from 1-50% total phosphate-containingbuilder, wherein at least 2% by weight of the total phosphate-containingbuilder comprises the condensed phosphates of the multifunctionaldetergent material.

2. Inorganic non-phosphate builders, including alkali metal silicates,carbonates (including bicarbonates and sesquicarbonates), citrates, andaluminosilicates. Aluminosilicate builders include those having theempirical formula: M_(z)(zAlO₂)_(y).vH₂O wherein z and y are integers ofat least 6, the molar ratio of z to y is in the range from 1.0 to about0.5, and v is an integer from about 15 to about 264. Thealuminosilicates can be crystalline or amorphous in structure and can benaturally-occurring aluminosilicates or synthetically derived, andpreferred synthetic crystalline aluminosilicate ion exchange materialsinclude Zeolite A, Zeolite P (B), Zeolite MAP and Zeolite X. Anespecially preferred embodiment is the crystalline aluminosilicate ionexchange material known as Zeolite A, having the formulaNa₁₂((AlO₂)₁₂(SiO₂)₁₂).vH₂O wherein v is from about 20 to about 30,especially about 27.

3. Organic detergent builders, including polycarboxylate buildercompounds having a plurality of carboxylate groups, preferably at least3 carboxylates. Other suitable polycarboxylates are disclosed in U.S.Pat. No. 4,144,226, Crutchfield et al., issued Mar. 13, 1979 and in U.S.Pat. No. 3,308,067, Diehl, issued Mar. 7, 1967. See also Diehl U.S. Pat.No. 3,723,322.

Other optional ingredients that can be included in the compositions caninclude:

1. Chelating agents, selected from the group consisting of aminocarboxylates, amino phosphonates, polyfunctionally-substituted aromaticchelating agents and mixtures thereof, and preferably selected fromethylenediamine tetracetates, N-hydroxyethylethylenediaminetriacetates,nitrilotriacetates, ethylenediamin e tetraproprionates,triethylenetetraamine hexacetates, diethylenetriamine pentaacetates,diethylenetriamine penta(methylene phosphonic acid), ethylenediaminetetra(methylene phosphonic acid), and mixtures and salts and complexesthereof. Such chelants can be included in the subject compositions at alevel up to about 5%, preferably from about 0.1% to about 2%, morepreferably from about 0.2% to about 1.5%, more preferably still fromabout 0.5% to about 1%.

2. Polymeric dispersing agents, including polymeric polycarboxylates,substituted (including quarternized and oxidized) polyamine polymers,and polyethylene glycols, such as: acrylic acid-based polymers having anaverage molecular of about 2,000 to about 10,000; acrylic/maleic-basedcopolymers having an average molecular weight of about 2,000 to about100,000 and a ratio of acrylate to maleate segments of from about 30:1to about 1:1; maleic/acrylic/vinyl alcohol terpolymers; polyethyleneglycol (PEG) having a molecular weight of about 500 to about 100,000,preferably from about 1,000 to about 50,000, more preferably from about1,500 to about 10,000; polyaspartate and polyglutamate;carboxymethylcellulose (CMC) materials; and water soluble or dispersiblealkoxylated polyalkyleneamine materials. These polymeric dispersingagents, if included, are typically at levels up to about 5%, preferablyfrom about 0.2% to about 2.5%, more preferably from about 0.5% to about1.5%. The substituted polyamine polymers are disclosed in WO 98/08928,published Mar. 5, 1998, incorporated herein by reference.

3. Polymeric soil release agent, or “SRA”, having hydrophilic segmentsto hydrophilize the surface of hydrophobic fibers such as polyester andnylon, and hydrophobic segments to deposit upon hydrophobic fibers andremain adhered thereto through completion of washing and rinsing cycles,thereby serving as an anchor for the hydrophilic segments. This canenable stains occurring subsequent to treatment with the SRA to be moreeasily cleaned in later washing procedures. Preferred SRA's includeoligomeric terephthalate esters; sulfonated product of a substantiallylinear ester oligomer comprised of an oligomeric ester backbone ofterephthaloyl and oxyalkyleneoxy repeat units and allyl-derivedsulfonated terminal moieties covalently attached to the backbone, forexample as described in U.S. Pat. No. 4,968,451, issued Nov. 6, 1990 toScheibel et al.; nonionic end-capped 1,2-propylene/polyoxyethyleneterephthalate polyesters of U.S. Pat. No. 4,711,730, issued Dec. 8, 1987to Gosselink et al.; an oligomer having empirical formula(CAP)₂(EG/PG)₅(T)₅(SIP)₁ which comprises terephthaloyl (T),sulfoisophthaloyl (SIP), oxyethyleneoxy and oxy-1,2-propylene (EG/PG)units and which is preferably terminated with end-caps (CAP), preferablymodified isethionates, as in an oligomer comprising onesulfoisophthaloyl unit, 5 terephthaloyl units, oxyethyleneoxy andoxy-1,2-propyleneoxy units in a defined ratio, preferably about 0.5:1 toabout 10:1, and two-end-cap units derived from sodium2-(2-hydroxyethoxy)-ethanesulfonate; oligomeric esters comprising: (1) abackbone comprising (a) at least one unit selected from the groupconsisting of dihydroxy sulfonates, polyhydroxy sulfonates, a unit whichis at least trifunctional whereby ester linkages are formed resulting ina branched oligomer backbone, and combinations thereof; (b) at least oneunit which is a terephthaloyl moiety; and (c) at least one unsulfonatedunit which is a 1,2-oxyalkyleneoxy moiety; and (2) one or more cappingunits selected from nonionic capping units, anionic capping units suchas alkoxylated, preferably ethoxylated, isethionates, alkoxylatedpropanesulfonates, alkoxylated propanedisulfonates, alkoxylatedphenolsulfonates, sulfoaroyl derivatives and mixtures thereof. Preferredare esters of the empirical formula:

((CAP)_(a)(EG/PG)_(b)(DEG)_(c)PEG)_(d)(T)_(e)(SIP)_(f)(SEG)_(g)(B)_(h))

wherein CAP, EG/PG, PEG, T and SIP are as defined hereinabove, DEGrepresents di(oxyethylene)oxy units, SEG represents units derived fromthe sulfoethyl ether of glycerin and related moiety units, B representsbranching units which are at least trifunctional whereby ester linkagesare formed resulting in a branched oligomer backbone, a is from about 1to about 12, b is from about 0.5 to about 25, c is from 0 to about 12, dis from 0 to about 10, b+c+d totals from about 0.5 to about 25, e isfrom about 1.5 to about 25, f is from 0 to about 12; e +f totals fromabout 1.5 to about 25, g is from about 0.05 to about 12; h is from about0.01 to about 10, and a, b, c, d, e, f, g, and h represent the averagenumber of moles of the corresponding units per mole of the ester; andthe ester has a molecular weight ranging from about 500 to about 5,000.;and; cellulosic derivatives such as the hydroxyether cellulosic polymersavailable as METHOCEL® from Dow; the C₁-C₄ alkyl celluloses and C₄hydroxyalkyl celluloses, see U.S. Pat. No. 4,000,093, issued Dec. 28,1976 to Nicol et al., and the methyl cellulose ethers having an averagedegree of substitution (methyl) per anhydroglucose unit from about 1.6to about 2.3 and a solution viscosity of from about 80 to about 120centipoise measured at 20° C. as a 2% aqueous solution. Such materialsare available as METOLOSE SM100® and METOLOSE SM200®, which are thetrade names of methyl cellulose ethers manufactured by Shinetsu KagakuKogyo KK

4. Enzymes, including proteases, amylases, lipases, cellulases, andperoxidases, as well as mixtures of two or more thereof. Suitableexamples of proteases are the subtilisins which are obtained fromparticular strains of B. subtilis and B. licheniforms. Another suitableprotease is obtained from a strain of Bacillus, having maximum activitythroughout the pH range of 8-12, developed and sold by Novo IndustriesA/S under the registered trade name ESPERASE®. The preparation of thisenzyme and analogous enzymes is described in British PatentSpecification No. 1,243,784 of Novo. Proteolytic enzymes suitable forremoving protein-based stains that are commercially available includethose sold under the tradenames ALCALASE® and SAVINASE® by NovoIndustries A/S (Denmark) and MAXATASE® by International Bio-Synthetics,Inc. (The Netherlands). Other proteases include Protease A (see EuropeanPatent Application 130 756, published Jan. 9, 1985) and Protease B (seeEuropean Patent Application 251 446, published Jan. 7, 1988). Amylasesinclude, for example, α-amylases described in British PatentSpecification No. 1,296,839 (Novo), RAPIDASE®, InternationalBio-Synthetics, Inc. and TERMAMYL®, Novo Industries. Amylase ispreferably included in the subject compositions such that the activityof the amylase is from about 0.02 KNU to about 5 KNU per gram of thecomposition, more preferably from about 0.1 KNU to about 2 KNU, morepreferably still from about 0.3 KNU to about 1 KNU. (KNU is a unit ofactivity used commercially by Novo Ind.) The cellulases usable in thesubject compositions include both bacterial and fungal cellulase.Preferably, they will have a pH optimum of between 5 and 9.5. Suitablecellulases are disclosed in U.S. Pat. No. 4,435,307, Barbesgoard et al.,issued Mar. 6, 1984, which discloses fungal cellulase produced fromHumicola insolens and Humicola strain DSM1800, a cellulase 212-producingfungus belonging to the genus Aeromonas, and cellulase extracted fromthe hepatopancreas of a marine mollusk (Dolabella Auricula Solander).Suitable cellulases are also disclosed in British Patent Spec. Nos.2,075,028 and 2,095,275 and German Patent Spec. No. 2,247,832.Cellulases disclosed in PCT Patent Application No. WO 91/17243, such asCAREZYME® (Novo), are especially useful cellulases. Cellulase ispreferably included in the subject compositions such that the activityof the cellulase is from about 0.1 CEVU to about 20 CEVU per gram of thecomposition, more preferably from about 1 CEVU to about 10 CEVU, morepreferably still from about 2 CEVU to about 5 CEVU. (The activity of acellulase material (CEVU) is determined from the viscosity decrease of astandard CMC solution as follows. A substrate solution is prepared whichcontains 35 g/l CMC (Hercules 7 LFD) in 0.1 M tris buffer at pH 9.0. Thecellulase sample to be analyzed is dissolved in the same buffer. 10 mlsubstrate solution and 0.5 ml enzyme solution are mixed and transferredto a viscosimeter (e.g., Haake VT 181, NV sensor, 181 rpm), thermostatedat 40° C. Viscosity readings are taken as soon as possibly after mixingand again 30 minutes later. The activity of a cellulase solution thatreduces the viscosity of the substrate solution to one half under theseconditions is defined as 1 CEVU/liter.) Suitable lipase enzymes fordetergent usage include those produced by microorganisms of thePseudomonas group, such a Pseudomonas stutzeri ATCC 19.154, as disclosedin British Patent 1,372,034. See also lipases in Japanese PatentApplication 53/20487, laid open to public inspection on Feb. 24, 1978.This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya,Japan, under the trade name Lipase P. Other commercial lipases includeAmano-CES, lipases ex Chromobacter viscosum, e.g., Chromobacter viscosumvar. lipolyticum NRRLB 3673, commercially available from Toyo Jozo Co.,Tagata, Japan; and further

Chromobacter viscosum lipases from U.S. Biochemical Corp., U.S.A. andDisoynth Co., The Netherlands, and lipases ex Pseudomonas gladioli. TheLIPOLASE® enzyme derived from Humicola lanuginosa and commerciallyavailable from Novo (see also EP 341 947) is a preferred lipase. Lipaseis preferably included in the subject compositions such that theactivity of the lipase is from about 0.001 KLU to about 1 KLU per gramof the composition, more preferably from about 0.01 KLU to about 0.5KLU, more preferably still from about 0.02 KLU to about 0.1 KLU. (KLU isa unit of activity used commercially by Novo Ind.) Peroxidase enzymesare used in combination with oxygen sources, e.g., percarbonate,perborate, persulfate, hydrogen peroxide, etc. They are used for“solution bleaching”, i.e. to prevent transfer of dyes or pigmentsremoved from substrates during wash operations to other substrates inthe wash solution. Peroxidase enzymes are known in the art, and include,for example, horseradish peroxidase, ligninase, and haloperoxidase suchas chloro- and bromo-peroxidase. Peroxidase-containing detergentcompositions are disclosed, for example, in PCT InternationalApplication WO 89/099813, published Oct. 19, 1989, by Kirk, assigned toNovo Industries ANS. The subject compositions typically comprise up toabout 5%, preferably from about 0.01% to about 2%, more preferably about0.2% to about 1%, of commercial enzyme preparations.

5. Bleaching compounds, including bleaching agents and bleach, includingperborate bleaches, e.g., sodium perborate (e.g., mono- ortetra-hydrate); percarboxylic acid bleaching including magnesiummonoperoxyphthalate hexahydrate, the magnesium salt of metachloroperbenzoic acid, 4-nonylamino4-oxoperoxybutyric acid anddiperoxydodecanedioic acid; peroxygen bleaching agents including sodiumcarbonate peroxyhydrate and equivalent “percarbonate” bleaches, sodiumpyrophosphate peroxyhydrate, urea peroxyhydrate, and sodium peroxide;persulfate bleach (e.g., OXONE®, manufactured commercially by DuPont);bleach activators, which lead to the in situ production in aqueoussolution (i.e., during the washing process) of the peroxy acidcorresponding to the bleach activator, such as nonanoyloxybenzenesulfonate (NOBS) and tetraacetyl ethylenediamine (TAED) activators aretypical, and mixtures thereof. When present, bleaching agents willtypically be at levels up to about 20%, preferably from about 1% toabout 5%, of the subject compositions. If present, the amount of bleachactivators will typically be up to about 70%, preferably from about 0.5%to about 5% of the subject compositions.

6. Fabric softening clay, such as a smectite-type clay.

7. Dye transfer inhibiting (DTI) ingredients, which prevent diminishingof color fidelity and intensity in fabrics, including hydrogen peroxideor a source of hydrogen peroxide, polyvinyipyrridine N-oxide,polyvinylpyrrolidone (PVP), PVP-polyvinylimidazole copolymer, copolymersof N-vinylpyrrolidone and N-vinylimidazole polymers (referred to as“PVPI”), and mixtures thereof. The amount of DTI included in the subjectcompositions, if any, is about 0.05%-5%, preferably about 0.2%-2%.

8. Photobleaches, particularly phthalocyanine photobleaches which aredescribed in U.S. Pat. No. 4,033,718 issued Jul. 5, 1977, incorporatedherein by reference, and preferably zinc and aluminum phthalocyaninecompounds, available under the tradename TINOLUX® and QUANTUM® (CibaGeigy). The photobleach components, if included, are typically in thesubject compositions at levels up to about 0.02%, preferably from about0.001% to about 0.015%, more preferably from about 0.002% to about0.01%.

9. Fillers, optionally used in addition to any filter function providedby the MFDM, such as sodium sulfate, calcium carbonate (Calcarb), talcand hydrated magnesium silicate-containing minerals. Optional additionalfiller material, if included, is typically at levels up to about 60%.

10. Optical brighteners, including derivatives of stilbene, pyrazoline,coumarin, carboxylic acid, methinecyanines, dibenzothiphene-5,5-dioxide,azoles, 5- and 6-membered ring heterocycles, and other miscellaneousagents, and preferably brighteners identified in U.S. Pat. No.4,790,856, issued to Wixon on Dec. 13, 1988, that included thePHORWHITE® series of brighteners from Verona; TINOPAL UNPA®, TINOPALCBS® and TINOPAL 5BM®, TINOPAL AMS-GX®, available from Ciba-Geigy; ARTICWHITE CC® and ARTIC WHITE CWD®, available from Hilton-Davis, located inItaly; the 2-(4-stryl-phenyl)-2H-napthol[1,2-d]triazoles;4,4′-bis-(1,2,3-triazol-2-yl)stilbenes; 4,4′-bis(stryl)bisphenyls; andthe aminocoumarins. Specific examples of these brighteners include4-methyl-7-diethylamino coumarin; 1,2-bis(-benzimidazol-2-yl)ethylene;1,3-diphenyl-phrazolines; 2,5-bis(benzoxazol-2-yl)thiophene;2-stryl-napth-[1,2d]oxazole;2-(stilbene-4-yl)-2H-naphtho-[1,2-d]triazole; and most preferably4,4′-bis((4-anilino-6-bis(2-hydoxyethyl)-amino-1,3,5-trizin-2-yl)amino)stilbene-2,2′-disulfonicacid disodium salt, 4-4′-bis(2-sulfostyryl)biphenyl (Br2) and4,4′-bis((4-anilino-6-morpholino-1,3,5-triazin-2-yl)-amino)stilbene-2,2′-disulfonicacid disodium salt. Such optical brighteners, or mixtures thereof, ifincluded, are typically at levels in the compositions up to about 1%,preferably about 0.01%-0.3%.

11. Water and solvents: The granular laundry and cleaning compositionsof the subject invention, including laundry bars, typically comprisefrom about 1% to about 25% water total moisture (free moisture andhydrate moisture), preferably from about 4% to about 15% water, morepreferably from about 5% to about 9% water. The amount of moisture willdepend upon the level of hydration of the inorganic salts in thecomposition. Aqueous liquid laundry and cleaning compositions typicallywill contain from about 5% to about 95% water, depending upon theconcentration of actives and other solvents. Other solvents can includethe aforementioned detergent surfactants, as well as monohydric andpolyhydric alcohols, and polymers.

12. Miscellaneous ingredients can include dyes, pigments, germicides,perfumes, polyethylene glycol, glycerine, sodium hydroxide,alkylbenzene, fatty alcohol, and other minors, some of which areimpurities carried in from surfactant-making processes, can also beincorporated in the subject compositions. If included, they aretypically at levels up to about 3%.

Processing of Laundry and Cleaning Products Containing MFDM

The MFDM of the present invention can be processed into laundry andcleaning products in manners very similar to conventional functionalmaterials.

In a first method of making a laundry or cleaning product containing aMFDM, the MFDM in a powdered or particulate form can be dry mixed withother powdered ingredients and then further mixed with liquid componentsincluding anionic surfactant pastes, water, and liquid polymers, into ahomogenous viscous detergent slurry. The viscous slurry can then bespray dried in a conventional spray tower by spraying the slurry asslurry droplets into a drying tower along with counter- or co-currenthot air, to remove moisture from the sprayed slurry droplet, therebyforming substantially dry porous detergent granules (also known as basegranules) having a bulk density of about 450 g/liter or less. Suchspray-drying systems and methods of preparing detergent slurries andspray-drying the detergent slurries to make base granules are wellknown, and are disclosed in U.S. Pat. Nos. 3,629,951 and 3,629,955(Davis et al.), U.S. Pat. No. 4,083,813 (Wise et al.), U.S. Pat. No.4,006,110 (Kenney et al.), and U.S. Pat. No. 4,129,511 (Ogoshi et al.),all such references herein incorporated by reference. The base granulescontaining or made using the MFDM can then be dry mixed with otherparticulate and powdered detergent components, such as enzymes andbleaches, or contacted with minor levels of spray-added ingredients suchas perfumes and functional polymers to form a detergent product, or canbe further processed, such as by compaction, grinding, agglomeration, orcompression, to form detergent particles of a different size, shape,porosity, and/or structure.

The mixing of MFDM into the slurry and then spray drying of the slurryinto a base granule can expose the MFDM to both moisture and hightemperature. Depending on the amount of time the MFDM remains in theslurry state, and on the temperatures of the slurry and the resultingbase granules produced by spray drying, a significant amount of thelinear polyphosphates and cyclic metaphosphates can be hydrolyzed tolower molecular weight condensed phosphate species, includingtripolyphosphate and pyrophosphate. Under ordinary slurrying andspray-drying conditions, much of, though not necessarily all, of thelinear polyphosphates and cyclic metaphosphates can be hydrolyzed to thelower molecular weight condensed phosphate species. Since the MFDM canbe used in large amounts in a detergent composition, even if thepolyphosphate material hydrolyses to an significant extent to, forexample, pyrophosphate and orthophosphate, there still remains asufficient amount of the polyphosphate material to prevent a loss inbuilder performance due to the “pyro dip”.

In a second method of making a laundry or cleaning product containing aMFDM, the MFDM in a powdered or particulate form can be optionally mixedwith other powdered ingredients, and mixing with a binder liquid in anenergy-intensive mixer to form agglomerates. The binder liquid caninclude an anionic, nonionic, or other detergent surfactant paste, waterglass (silicate), water, and liquid polymers. Optional other powderedingredients can include, but are not limited to, aluminosilicates,layered silicates, carbonate, bicarbonate, and softening clays, as wellas spray-dried detergent powders. The agglomeration can be conducted inthe following preferred mixers, alone or in combination with othermixers, and either in a batch or continuous process: an Elrich Type RIntensive Mixer, a Littleford mixer, a Lodige type CB Mixer, and aLodige type KM Mixer. Other equipment that can also be used toagglomerate the dry mixture with a liquid binder includes a schugi mixerand an O'Brien mixer, as well as any of the known fluid bedagglomerating systems. Such processes are described in the followingU.S. Patents, and are incorporated herein by reference: U.S. Pat. No.5,009,804 (Clayton et al.); U.S. Pat. No. 5,108,646 (Beerse et al.);U.S. Pat. No. 5,489,392 (Capeci et al.); U.S. Pat. No. 5,496,487 (Capeciet al.); U.S. Pat. No. 5,494,599 (Goovaerts et al.); and U.S. Pat. No.5,616,550 (Kruse et al.).

In another method of making a laundry or cleaning product containing aMFDM, the MFDM in a powdered or particulate form can serve an alkalineagent in a dry neutralization process, whereby the MFDM is mixed with aliquid anionic detergent acid in an energy-intensive mixer, therebyneutralizing the detergent acid and forming an agglomerate containingthe corresponding anionic detergent surfactant. In such a process, theMFDM is either the principle or a co-alkaline agent, replacing orsupplementing more conventional alkaline agents such as sodiumcarbonate, sodium bicarbonate, and sodium metasilicate. Depending on thereserve alkalinity in the MFDM, and on the proportion of anionicdetergent acid to be neutralized, an amount of aqueous sodium hydroxideor sodium carbonate, or other alkaline source, can be added with theMFDM to ensure complete and rapid neutralization of the detergent acidto the anionic detergent surfactant. The neutralization andagglomeration can be conducted in the following preferred mixers, aloneor in combination with other mixers, and either in a batch or continuousprocess: an Elrich Type R Intensive Mixer, a Littleford mixer, a Lodigetype CB Mixer, and a Lodige type KM Mixer. Such processes are describedin the following U.S. Patents, and are incorporated herein by reference:U.S. Pat. No. 2,688,035 (Jacob et al.); GB Patent 1,369,269(Colgate-Palmolive); U.S. Pat. No. 4,587,029 (Brooks); U.S. Pat. No.4,919,847 (Barletta et al.); U.S. Pat. No. 5,164,108 (Appel et al.);European Patent 352,135 (Unilever); U.S. Pat. No. 5,527,489 (Tadsen etal.); and U.S. Pat. No. 5,573,697 (Riddick et al.).

ANALYTICAL METHODS

a) Ion Chromatography of Polyphosphates

Principles and Scope

The characterization of the distribution of polyphosphates andmetaphosphates (referred to collectively within this method aspolyphosphates) in a MFDM was carried out by ion chromatography (IC)with suppressed conductivity detection. In IC, the separation of thepolyphosphate components is achieved when an aqueous solution of thesample carried by the alkaline mobile phase (or eluant) is passedthrough an anion exchange packing (stationary phase composed of apolymeric resin bed that contains functionalized active sites) containedin the chromatographic column. In the column the sample componentsmigrate and interact with the stationary phase. The migration of a givenanion is a function of the equilibrium distribution of the samplebetween the mobile and the stationary phase. Components havingdistributions favoring the stationary phase migrate more slowly thanthose having distributions favoring the mobile phase. Separationtherefore results from different migration rates as a consequence of theequilibrium distribution or components affinity for either of the twophases. Usually, the chemistry between the stationary and the mobilephases is different enough that the analyte will interact with one phasemore than the other. It is this discrepancy which enables the separationto take place. For the case of polyphosphates the molecular size of thepolyphosphates favor their retention in the stationary phase so theorder of elution is proportional to the phosphate chain size.

The detection of the condensed phosphate peaks is achieved in aconductivity detector where the present of more ions in the solutionpassing through detector cell, will allow more electrical current toflow between the charged electrodes, resulting in current peaksproportional to the concentration of conductive species in the solution.The sensitivity of the detector is significantly improved by suppressingthe background conductivity of the mobile phase just before passingthrough the detector. This is achieved using an anion self-regeneratingsuppression system.

Instrument Operation

Flow rate: 2.0 ml/min.

Pre-run Column Equilibration

Eluant stand by 35% 200 mM NaOH, 65% H₂O 0.1 min 8% 200 mM NaOH, 92% H₂O5 min 8% 200 mM NaOH, 92% H₂O

Chromatographic Run

Eluant Initial (inject sample) 8% 200 mM NaOH, 92% H₂O  2 min 8% 200 mMNaOH, 92% H₂O  90 min 50% 200 mM NaOH, 50% H₂O 100 min 35% 200 mM NaOH,65% H₂O Detector Background conductivity, 3 uS (approx.) Range 30 uSSuppressor Flow 3-4 mL/min Suppressor 500 mA Temperature Compensation1.7° C. Analysis run time 100.0 minutes

Quantitation of % Polyphosphates from the IC Chromatograms

The composition in weight percentages of the different polyphosphates iscalculated using Peak Area/weight of P₂O₅ response factors obtainedusing sodium pyrophosphate, metaphosphate and tripolyphosphateanalytical standards adjusted for the total P₂O₅ level present in thematerial.

b) X-Ray Diffraction

Principles and Scope

The identification of a crystalline component of MFDM is carried out byX-Ray Diffraction (XRD). It is well known that when crystallinematerials are bombarded with x-rays, scattering patterns are produced.If a monochromatic x-ray beam falls on a powder crystalline sample, thebeam is reflected by each of the crystal planes. Each separate reflectedbeam interacts with the other reflected beams. If the beams are not inphase, they destroy each other, hence no x-ray emerges. If the beams arein phase (coherent), the net result is a diffraction pattern. Coherenceoccurs, as described by the Bragg equation, when nλ=2dsin θ, where nλ=whole number of x-ray wavelength, d=spacing between the crystal plane,and θ=angle of incidence.

For a given powder XRD experiment conducted on a Bragg-Brentanodiffractometer, one varies the angle between the X-ray tube and amonochromator, which serves as the detector. The resultant pattern is aplot of the diffraction intensities (in counts per second) as a functionof the angle (2θ). Qualitative identification of the crystallinecomponents are then obtained by matching the resultant pattern topreviously identified standard patterns. If the sample is multiphase,the pattern is just a superimposed pattern of the individual components.It is also possible to estimate the amount of amorphous content of asample, since this type of scattering gives rise to an increasedbaseline.

Qualitative Identification

A Bragg-Brentano style diffractometer is used to identify thecrystalline component. The sample is top packed into an Anton Parr TTKsample holder. The program used to analyze the sample is a normal,coupled, continuous scan from 1 to 40° 2θ, 2.0 second count time, 0.02°step size at room temperature. The pattern is generated and theidentified of the crystalline components matched against standards inthe JCPDS database.

c) P₂O₅ and SiO₂

The level of total P205 in a MFDM and in base granules can be determinedby converting all available phosphate species to ortho-phosphate form byacid hydrolysis. This ortho-phosphate is reacted with molybdate in theacid solution and then quantified colorimetrically measuring the bluecomplex formed by reduction of phosphomolybdate with hydrazine sulfate.The level of SiO₂ in both MFDM and base granules can be determined byatomic absorption spectrophotometry directly in a alkaline dissolutionof the sample.

To enable the persons having ordinary skill in the art to carry out theprocess of the above described invention, the following examples, takenin relation with the description herein, are provided only by way ofinformation about the viability of this invention, but withoutconsidering that the final product could be used for a specificdetergent formulation.

EXAMPLE 1

Ground trona ore, silica sand, and treated (acid attacked) phosphoricrock of known active levels of Na₂O, SiO₂, and P₂O₅, are mixed andhomogenized in a mixer to produce a particulate batch having thefollowing weight ratio of the inorganic oxides: 2 P₂O₅:2 Na₂O:1 SO₂.

This batch is fed to a rotary kiln and is reacted at a temperature ofabout 800° C. for about 1 hour, and is then fed to a furnace to melt thereacted batch at a temperature of about 1200° C. for about 3 hour, toproduce one ton of a molten glass product. The molten glass product iscooled with water to form cullet, which is then ground intodetergent-size particles of the resulting multifunctional detergentmaterial powder.

EXAMPLE 2

The detergent-size particles of the MFDM of Example 1 are used toprepare a detergent product using a standard spray-drying process formaking detergent base granules. A crutcher mix slurry is prepared bymixing together the following liquid and solid ingredients in thefollowing order, to form a slurry at 60 degrees C.: 45 parts C₁₈ linearalkylbenzene sulfonate (LAS) paste (40% active), 0.5 parts linearC₁₂-C₁₄ dimethyl hydroxyethyl quaternary ammonium chloride, 1.5 partsalkyl ethoxy (E3) sulfate paste (30% active), 21.5 parts of the MFDM ofExample 1, and 47.5 parts sodium sulfate. The slurry mixture isdischarged through a series of atomizing nozzles into a spray-dryingtower and contacted with a counter-current stream of hot drying air (240degrees C.), to provide spray-dried granular detergent base granuleshaving a moisture content (loss at 135 degrees C. in 1 hour) of about8%. The base granules are admixed with minor amounts of perfume andenzyme, and 4 parts carbonate, to form a detergent product.

EXAMPLE 3

A MFDM of the present invention was made according to the process of thepresent invention, having an approximate weight ratio of the inorganicoxides of about 9 P₂O₅:8 Na₂O:3 SiO₂. The MFDM was analyzed using IonChromatography according to the method herein described. FIG. 1 shows anIon Chromatogram of the MFDM. The material had a total of 45.1% P₂O₅,and 68.9% by weight condensed phosphate species. The condensed phosphatespecies were comprised, by weight, of about 90.9% higher polyphosphates(n>3), 1.8% STPP, 4.0% TSPP, 2.8% trimetaphosphate (cyclic, n=3), and0.5% orthophosphate. FIG. 2 shows the X-Ray Diffraction pattern for theMFDM, which has been identified as crystalline sodium silicate (Card No.16-0818). The ratio of linear polyphosphate to cyclic metaphosphates wasabout 8.6:1. The material also had a reserve alkalinity of about 35.9 gmNaOHI100 cc material, and 15.24% SiO₂.

EXAMPLE 4

The MFDM of Example 3 was processed into a base granule compositiongenerally in accordance with the method described in Example 2. The basegranules with the MFDM processed thereinto were analyzed using IonChromatography according to the method herein described. FIG. 3 shows anIon Chromatogram of the base granule containing the MFDM. The materialhad a total of 17.3% P₂O₅, and 32.2% by weight condensed phosphatespecies. The condensed phosphate species in the base granule werecomprised, by weight, of about 9.9% higher polyphosphates (n>3), 6.5%STPP, 61.3% TSPP, 0.0% trimetaphosphate (cyclic, n=3), and 22.3%orthophosphate.

The processing of the MFDM by slurrying and spray-drying to form basegranules, results in the hydrolysis of a portion of the polyphosphatematerial contained in the MFDM to lower polyphosphates, primarily TSPP.The chromatogram of FIG. 3 shows a remaining portion of thepolyphosphate in the base granules. The base granule containing the MFDMprocessed therein provides effective sequestration of hardness in washsolutions.

It is to be understood that the above products and processes areprovided only as specific embodiments of the invention and that thepersons having ordinary skill in the art will be able. with theteachings of herein disclosed, to carry out different performingexamples with different ratios and steps, which will be within the truescope of the invention as defined in the following claims.

What is claimed is:
 1. A multifunctional detergent material comprising acondensed phosphate component selected from the group consisting of: (i)linear polyphosphates of the formula I

 where n is from 3-100, and where M is selected from Na, K, Li, and H,and mixtures thereof; (ii) cyclic metaphosphates of the formula II

 where n is from 3-20, and where M is selected from Na, K, Li, and H,and mixtures thereof; and mixtures thereof; and a silicate componentcomprising silicon oxide (SiO₂) and sodium oxide and wherein thecondensed phosphate component and the silicate component are miscibleand form a solid solution.
 2. The multifunctional detergent materialaccording to claim 1 wherein the condensed phosphate component is thesolid continuous phase and the silicate component is the solid phasedispersed within the continuous phosphate component.
 3. Themultifunctional detergent material according to claim 1 wherein thecondensed phosphate component is amorphous.
 4. The multifunctionaldetergent material according to claim 3 wherein the silicate componentis crystalline.
 5. The multifunctional detergent material according toclaim 1 wherein the weight ratio of P₂O₅ to SiO₂ is from about 1:20 toabout 12:1.
 6. A laundry detergent composition comprising, by weight: a)from 1-45% a detergent surfactant, and b) from 3-95% a multifunctionaldetergent material comprising a condensed phosphate component selectedfrom the group consisting of (i) linear polyphosphates of the formula I

 where n is from 3-100, and where M is selected from Na, K, Li, and H,and mixtures thereof; (ii) cyclic metaphosphates of the formula II

 where n is from 3-20, and where M is selected from Na, K, Li, and H,and mixtures thereof; and mixtures thereof; and a silicate componentcomprising silicon oxide (SiO₂) and sodium oxide, and wherein thecondensed phosphate component and the silicate component are miscibleand form a solid solution.
 7. The laundry detergent composition of claim5 wherein the condensed phosphate component is amorphous phosphate andthe silicate component is crystalline silicate.
 8. A laundry detergentcomposition comprising, by weight: a) from 1-45% detergent surfactant,and b) from 1%-50% of phosphate-containing builder, wherein at least 2%by weight of the phosphate-containing builder comprises amultifunctional detergent material comprising a condensed phosphatecomponent selected from the group consisting of (i) linearpolyphosphates of the formula I

 where n is from 3-100, and where M is selected from Na, K, Li, and H,and mixtures thereof; (ii) cyclic metaphosphates of the formula II

 where n is from 3-20, and where M is selected from Na, K, Li, and H,and mixtures thereof; and mixtures thereof; and a silicate componentcomprising silicon oxide (SiO₂) and sodium oxide, and wherein thecondensed phosphate component and the silicate component are miscibleand form a solid solution.
 9. A laundry detergent compositioncomprising, by weight: a) from 1-45% detergent surfactant, and b) from3%-50% of a condensed phosphate component selected from the groupconsisting of (i) linear polyphosphates of the formula I:

 where n is from 4-100, and where M is selected from Na, K, Li, and H,and mixtures thereof; (ii) cyclic metaphosphates of the formula II:

 where n from 3-20, and where M is selected from Na, K, Li, and H, andmixtures thereof; and mixtures thereof and wherein the condensedphosphate component and the silicate component are miscible and form asolid solution.